Method of dyeing



Patented Feb. 12, 1946 METHOD OF DYEING Karl Heyman, Montclalr, N. J.,assignor to American Viscose Corporation, Wilmington, Del., acorporation of Delaware No Drawing. Application January 7, 1944, SerialN0. 517,433

16 Claims. (Cl. 8-55) This invention relates to improvements in methodsof dyeing yarns and other shaped articles comprising materials that arenot readily permeable to water. More particularly, the invention relatesto improvements in methods of dyeing yarns and other shaped articlescomprising vinyl, polymers, such as polymers of vinyl chloride andcopolymers of vinyl acetate with vinyl chloride.

This application is a continuation-in-part of my applications SerialNos. 319,020, filed February 15, 1940, and 322,844 filed March 7, 1940,which are in turn continuations-in-part of Serial No. 311,109, filedDecember 27, 1939.

Materials that are not readily permeable to water cannot besatisfactorily dyed by the ordinary dyeing procedure used in dyeingcotton, wool, natural silk and regenerated cellulose. When ordinarymethods of dyeing are attempted, the dye either does not penetrate thematerial and no dyeing is effected, or when dyeing is effected the coloris not fast and leaches out.

Yarns and other shaped articles, such as those of cellulose acetate,which are not readily permeable to water have been dyed when treatedwith a liquid swelling agent, such as alcohol, acetone or acetic acid.The swelling agent apparently forms or opens pores in the material intowhich the dye penetrates. There are certain objections to the use ofliquid swelling agents. Generally a large amount of swelling agent isrequired. Also the swelling agent has a tendency to weaken the yarn orshaped articles.

I have discovered that yarns and other shaped articles comprising vinylpolymers, such as polymers of vinyl chloride and copolymers of vinylacetate with vinyl chloride, can be successfully dyed with suspensiondyestuffs when the dyeing operation is carried out with aqueoussuspensions of the dyestufis in the presence of certain normally solidwater-insoluble organic compounds which have a solubility in the vinylpolymers of 2% or greater under the conditions at which the dyeing iscarried out. By the term "suspension dyestuffs is meant water-insolubledyestuffs of the type applicable to cellulose acetate from a dispersion(insoluble anthraquinone and azo dyes) sometimes referred to asdispersol dyes, and the dyestuffs referred to hereinafter in theexamples by their trade names, are of this type. The compounds which arereferred to as assistants include:

Diphenyl Naphthalene Phenanthrene a-Naphthol b-Naphthol Thio-b-naphthol2,4-dichloro-a-naphthol 2,4-dibromo-a-naphthol o-Hydroxydiphenyl2-chloro-6-phenylphenol 4-chloro-6-phenylphenol o-Cyclohexylphenolp-Chlorothymol 2,4-dichloroaniline 2,5-dichloroaniline a-Naphthylamineb-Naphthylamine Phenyl-a-naphthylamine Phenyl-b-naphthylamineo-Aminodiphenyl Desoxybenzoin Fluorenone 4-chlorobenzophenones-hydroxyquinoline Dibenzyl succinate Methyl-p-bromobenzoate Diphenylphthalate b-Naphthyl acetate Phenyl glycine ethylester Diphenylcarbonate Di-o-cresyl carbonate 2,4,6-tribromophenyl acetate a-Naphthylacetate o-Diphenyl acetate Ethylene dibenzoate Glycerol tribenzoatep-Aminodiphenyl N,N-diphenyl ethyl carbamate b-Naphthonitrilep-Chlorobenzaldehyde 2,4-dimethoxybenzaldehydep-Dimethylaminobenzaldehyde o-Hydroxyacetophenone Benzophenonep-Hydroxybenzophenone Methyl-b-naphthylketone Camphor BenzalacetoneAnisalacetone Benzoylacetone Benzalacetophenone 1-hydroxy-2-acetonaphthone p-Methoxybenzophenone Benzil DiphenyltriketoneDibenzoylmethane Benzhydrol Phenylbenzylcarbinol2.4-dichlorobenzophenone Fluorenyl alcohol b,b'-Diphenoxydiethyletherp-Methoxydiphenyl Benzyl-a-naphthylether b-Naphthylmethyletherp-Methoxybenzophenone Benzoic anhydride Dicyclohexyl phthalate Dibenzylphthalate Phenyl benzoate m-Cresyl benzoate p-Cresyl benzoate Incarrying out my improved method of dyeing an aqueous suspensioncontaining a single assistant or several assistants together may beused. The assistant is, for example, dissolved in a suitable solvent,such as alcohol, and the resulting solution and a suitable dispersingagent.

such as that known in the trade as I'gepon T, are added to the aqueousdye bath containing the suspension dyestufl. The assistant is thus orshaped article to be dyed is then treated with the dye bath containingthe assistant in anyoonventional manner. This procedure may be followedusing Various quantities of dyestufi and assistants with different dyebath ratios andtem- .t'dye bath was'also used with Cibacete Scarletperatures of the dye baths depending upon the character of the materialbeing dyed and the type of dyeing that is being carried out. Asatisfactory procedure is one in which the dye bath ratio is 1:30 andcontains 1.5% suspension dyestufl with 5% or less of the solidwater-insoluble assistant based on the weight of the yarn or shapedarticle to be dyed. A suitable dye bath temperature is about 50 C., andthe duration of the dyeing operation one hour. Other temperatures mayalso be used, provided the temperature does not exceed the shrinkagetemperature 01 the resin article being dyed.

My invention may also be carried out by preliminarily applying-theassistant from suspension directly to the yarn or shaped article. Whenthe yarn or shaped article is thereafter immersed in the dye bath, theassistant aids the action of the dye bath on the yarn or shape in thesame manner as when it has been added to the dye bath.

Instead of using either of the above methods, I may incorporate theassistant directly within the vinyl polymers before the yarn or othershaped article is formed. The yarn or shaped article containing theassistant is treated with the dye bath (to which no solid assistant needbe added) in the ordinary manner.

No satisfactory explanation for the effectiveness of the solidsubstances as dyeing assistants has been found. They are efiective inmuch smaller amounts than the liquid swelling agents heretofore used toassist penetration of the resin mass being dyed, about half toone-fourth as much or even less of the solid assistants being capable,in most cases, of producing a. given dyeing effect. They exertrelatively little if any swelling action upon the mass being dyed.Instead of being softened and weakened by subjection to the dye bath asin the case of the liquid swelling agents heretofore used, vinyl resinfibers immediately after removal from the dye bath show no appreciablesoftening and often have a harsh hand. The efiectiveness does not appearto depend on melting of the solid assistant during dyeing, the dyeingbeing assisted to approximately the same extent, regardless of whetherthe temperature of the dye bath is above or below the melting pointofthe assistant. It is surprising and unpredictable that a solidmaterial, even in the colloidally dispersed condition, would assistpenetration of a resin by an insoluble dyestufl. Besides increasedefliciency as compared to liquid swelling agents, the solid dyeing as-The following examples are illustrative of the invention:

Eaomple 1.-Yarns comprising copoers of vinyl acetate and vinyl chloridewere dyed in dye baths having a dye bath ratio or 1:30 and containing1.5% suspension dyestufi and 5% bnaphthol based on the weight of theyarn. The

.temperatures'oi the dye baths'were 60, 6.. and

the duration of the dyeing operation-one hour.

The dyestuffs that were used were Cibacete Orange 2R Qibacete Scarlet GAcele Violet B Y facele' Yellow 3G G 1% and Acele Violet B 1% as the dy.

Example 2.-Yarns comprising copolymersof vinyl acetate and vinylchloride were dyed in dye baths having a dye bath ratio of 1:30 andcontaining 1.5% suspension dyestufi and 5% p-Dimethylamino-benzaldehydebased on the weight of the yarn. The temperatures of the dye baths were60 C. and the duration of the dyeing operation one hour. The dyestuflsthat were used were Celliton Red Violet RR Phenacyl Navy Blue RVPhenacyl Red R Celutate Brill. Blue 3 Cibacete Rubine BS Artisil DirectYellow 3GP Example 3.Yarns comprising copolymers of vinyl acetate andvinyl chloride were dyed in dye baths having a dye bath ratio of 1:30and containing 1.5% suspension dyestuff and 1.5% benzophenone based onthe weight of the yarn. The temperatures of the dye baths were 60 C. andthe duration of the dyeing operation one hour. The dyestuffs that wereused were Celliton Fast Pink BA Acele Scarlet G Calconese Orange 3R0Cibacete Violet B Celutate Fast Blue GL Artisil Direct Yellow 36 ex.

Phenacyl Red R Example 4.-Yarns comprising copolymers of vinyl acetateand vinyl chloride were dyed in dye baths having a dye bath ratio of1:30 and containing 1.5% suspension dyestufi and 5% o-Hydroxydiphenylbased on the weight of the yarn. The temperatures of the dye baths were60 C. and the duration of the dyeing operation one hour. The dyestuffsthat were used were Celliton Pink RF Celliton Red BR Celliton Orange 3RNCibacete Yellow 2RN Celliton Fast Yellow GRA Cibacete Yellow 5G CibaceteBrill; Blue BGG Celliton Fast Blue FFRS Celliton Discharge Violet BCibacete Discharge Violet 5R Camacyl Brill. Green B Phenacyl Red RCibacete Violet B Artisll Direct Yellow 36? ex cone.- Celliton FastBrown 5RA Example 5.-Yarns comprising copolymers of vinyl acetate andvinyl chloride were treated with a bath in a ratio of 1:30 containing 5%o-hydroxydiphenyl based on the weight of the yarn at a temperature of 60C. and for a period of one-half hour. The yarns so treated were thendyed by immersing in dye baths having a dye bath ratio of 1:30 andcontaining 1.5% suspension dyestuff based on the weight of the yarn. Thetemperatures of the dye baths were '60 C. and the duration of the dyeingoperation one hour. The dyestufis that were used were Camacyl Brill.Green B Phenacyl Red R Cibacete Violet B Artisil Direct Yellow 3GP ex.cone. Celliton Fast Brown 5RA While preferred assistants and procedureshave been shown, it is to be understood that changes and variations maybe made without departing from the spirit and scope of the invention asdefined in the appended claims.

I claim:

1. A method of dyeing yarns and other shape articles comprising vinylpolymers, comprising the step of treating the yarn or shaped articlewith an aqueous dye bath containing a suspension dye stufi, in thepresence of a water-insoluble, normally solid organic compound selectedfrom the group consisting of o-hydroxyacetophenone, benzophenone,p-hydroxybenzophenone, methyl-bnaphthylketone, camphor, benzalacetone,anisalacetone, benzoylacetone, benzalacetophenone, l-hydroxy -2-acetonaphthone, p-methoxybenzophenone, benzil, diphenyltriketone,dibenzolylmethane, desoxybenzoin, fluorenone, 4-chlorobenzophenone,2.4-dichlorobenzophenne.

2. A method of dyeing yarns and other shaped articles comprisingcopolymers of vinyl acetate and vinyl chloride, comprisin the step oftreating the yarn or shaped articles with an aqueous dye bath containinga suspension dyestuif, in the presence of a water-insoluble, normallysolid organic compound selected from the group consisting ofo-hydroxyacetophenone, benzophenone, p-hydroxybenzophenone, methylb-naphthylke tone, camphor, benzalacetone, anisalacetone, benzoylacetone,benzalacetophenone, l-hydroxy- Z-acetonaphthone, p-methoxybenzophenone,benzil, diphenyltriketone, dibenzoylmethane, desoxybenzoin, fluorenone,4-chlorobenzophenone, 2.4- dichlorobenzophenone.

3. A method of dyeing yarns and other shaped articles comprising vinylpolymers, comprising the step of treating the yarn or shaped articleswith an agneous dye bath containing a suspension dyestuff and awater-insoluble, normally solid organic compound selected from the groupconsistin of 0 hydroxyacetophenone, benzophenone, p hy-' droxybenzophenone, methyl-b-naphthylketone, camphor, benzalacetone,anisalacetone, benzoylacetone, benzalacetophenone, 1 hydroxy 2acetonaphthone, p-methoxybenzophenone, benzil, diphenyltriketone,dibenzoylmethane, desoxybenzoin, fluorenone, 4-chlorobenz0phenone, 2.4-dichlorobenzophenone dispersed in the dye bath.

4. A method of dyeing yarns and other shaped articles comprisingcopolymers of vinyl acetate and vinyl chloride, comprising the step oftreating the yarn or shaped articles with an aqueous dye bath containinga suspension dyestuff and a water-insoluble, normally solid organiccompound renone, 4-chlor0benzophenone, 2.4-dichlorobenzophenonedispersed in the dye bath.

5. A method of dyeing yarns and other shaped articles comprising vinylpolymers, comprising the step of treating the yarn or shaped articleswith an aqueous dye bath containing a suspension dyestufi in thepresence of camphor.

6. A method of dyeing yarns and other shaped articlescomprising vinylpolymers, comprising the step of treating the yarn or shaped articleswith an aqueous dye bath containing a suspension dyestufi in thepresence of benzophenone.

'7. A method of dyeing yarns and other shaped articles comprising vinylpolymers, comprising the step of treating the yarn or shaped articleswith an aqueous dye bath containing a suspension dyestufi in thepresence of methyl-b-naphthylketone.

8. A method of dyeing yarns and other shaped articles comprisingcopolymers of vinyl acetate and vinyl chloride, comprising the step oftreating the yarn or shaped articles with an aqueous dye bath containinga, suspension dyestufi in the presence of camphor.

9. A method of dyeing yarns and other shaped articles comprisingcopolymers of vinyl acetate and vinyl chloride, comprising the step oftreating the yarn or shaped articles with an aqueous dye bath containinga suspension dyestuff in the presence of benzophenone.

10. A method of dyeing yarns and other shaped articles comprisingcopolymers of vinyl acetate and vinyl chloride, comprising the step oftreating the yarn or shaped articles with an aqueous dye bath containinga suspension dyestuff in the presence of methyl-b-naphthylketone.

11. A method of dyeing yarns and other shaped articles comprising vinylpolymers, comprising the step of treating the yarn or shaped articleswith an aqueous dye bath containing a suspension dyestuff and camphordispersed in the dye bath.

12. A method of dyeing yarns and other shaped articles comprising vinylpolymers, comprising the step of treating the yarn or shaped articleswith an aqueous dye bath containing a suspension dyestuif andbenzophenone dispersed in the dye bath.

13. A method of dyeing yarns and other shaped articles comprising vinylpolymers, comprising the step of treating the yarn or shaped articleswith an aqueous dye bath containing a suspension dyestufi andmethyl-b-naphthylketone dispersed in the dye bath.

14. A method of dyeing yarns and other shaped articles comprisingcopolymers of vinyl acetate and vinyl chloride, comprising the step oftreating the yarn or shaped articles with an aqueous dye bath containinga suspension dyestuff and camphor dispersed in the dye bath.

15. A method of dyeing yarns and other shaped articles comprisingcopolymers of vinyl acetate and vinyl chloride, comprising the step oftreating the yarn or shaped articles with an aqueous dye bath containinga suspension dyestufi and benzophenone dispersed in the dye bath.

16. A method of dyeing yarns and other shaped articles comprisingcopolymers of vinyl acetate and vinyl chloride, comprising the step oftreating the yarn or shaped articles with an aqueous dye bath containinga suspension dyestufr and.

methyl-b-naphthylketone dispersed in the dye bath.

KARL HEYMAN.

